US5393489A - High temperature, lead-free, tin based solder composition - Google Patents

High temperature, lead-free, tin based solder composition Download PDF

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Publication number
US5393489A
US5393489A US08/079,075 US7907593A US5393489A US 5393489 A US5393489 A US 5393489A US 7907593 A US7907593 A US 7907593A US 5393489 A US5393489 A US 5393489A
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US
United States
Prior art keywords
weight
solder
alloy
alloys
weight percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/079,075
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English (en)
Inventor
Stephen G. Gonya
James K. Lake
Randy C. Long
Roger N. Wild
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lockheed Martin Corp
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International Business Machines Corp
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Assigned to IBM CORPORATION reassignment IBM CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GONYA, STEPHEN G., LAKE, JAMES K., LONG, RANDY C., WILD, ROGER N.
Priority to US08/079,075 priority Critical patent/US5393489A/en
Priority to JP6081871A priority patent/JPH0788680A/ja
Priority to KR1019940011318A priority patent/KR970010891B1/ko
Priority to EP94108683A priority patent/EP0629466A1/en
Priority to TW083105956A priority patent/TW363334B/zh
Publication of US5393489A publication Critical patent/US5393489A/en
Application granted granted Critical
Assigned to LOCKHEED MARTIN CORPORATION reassignment LOCKHEED MARTIN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL BUSINESS MACHINES, CORPORATION
Assigned to LOCKHEED MARTIN CORPORATION reassignment LOCKHEED MARTIN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LOCKHEED MARTIN FEDERAL SYSTEMS, INC., INTERNATIONAL BUSINESS MACHINES CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262Sn as the principal constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10Details of semiconductor or other solid state devices to be connected
    • H01L2924/11Device type
    • H01L2924/12Passive devices, e.g. 2 terminal devices
    • H01L2924/1204Optical Diode
    • H01L2924/12044OLED

Definitions

  • the present invention relates to lead free, low toxicity solder alloys that are particularly useful in microelectronic applications.
  • the solder alloys of the invention which contain in excess of 90 weight percent Sn, and an effective amount of either (1) Ag and Bi, optionally with Sb or with Sb and Cu, or (2) Ag and Sb, optionally with Bi. These alloys are particularly useful in joining integrated circuit chips to chip carriers and substrates, as printed circuit boards, joining chip carriers to substrates, and joining circuitization lands and pads in multilayer printed circuit boards.
  • Soldering is a low temperature, generally reversible, metallurgical joining process. Low temperature and reversibility are especially important in electronics applications because of the materials involved and the necessity for reworking and making engineering changes.
  • Solder joining is a wetting process followed by a chemical reaction. Molten solder wets selectively. The selective wettability of solders allow molten solder to be confined to desired sites. This is especially important in flip chip bonding, and in working with solder masks.
  • soldering process can be accomplished as quickly as the wetting takes place, for example, on the order of a few seconds. This makes soldering particularly desirable for automated, high speed, high throughput processes.
  • Wettability is also a function of the materials to be joined, with Cu, Ni, Au, and Pd, as well as alloys rich in one or more of these metals, being particularly amenable to soldering.
  • the chemical reaction following wetting is between the molten solder and the joining metallurgy to form an intermetallic phase region at the interface.
  • the intermetallic phases formed by solders in electronic packaging are stoichiometric compounds, typically binary compounds, and typically containing Sn if Sn is present in the solder alloy.
  • the base, pad, or land is Cu
  • the solder alloy is rich is Sn
  • the intermetallic formed during soldering is Cu--Sn.
  • Exemplary Cu--Sn binaries include Cu 3 Sn and Cu 6 Sn 5 .
  • Solder alloys are characterized by the melting temperature being a strong function of composition. While a pure metal is characterized by a single, invariant, melting temperature, the freezing and melting points of alloys are complex.
  • the freezing point of an alloy is determined by the liquidus line. Above the liquidus line only a liquid phase or phases can exist.
  • the melting point of an alloy is determined by the solidus line. Below the solidus line only a solid phase or phases can exist. In the region between these two lines, i.e., between the liquidus line and the solidus line, solid and liquid phases can co-exist.
  • the preferred soldering alloys are eutectics, that is, they are characterized by a eutectic point.
  • the eutectic point is where the liquidus and solids lines meet. A concentration change in either direction from the eutectic results in an increase in the liquidus temperature.
  • the composition, and the quench rate also determine the microstructure and the resulting mechanical properties of the solder joint. Thus, it is necessary to both carefully choose the solder composition and to carefully control the thermal exposure of the soldered joint.
  • solder composition used in electronics fabrication must be wettable as a solder alloy, and have at least one component capable of forming an electrically conductive, thermally stable, non-brittle, plastic intermetallic with the pad or land metallurgy. For this reason, the most common solder alloys are lead based alloys, as Sn--Pb alloys.
  • Pb/Sn solders have been utilized for electronic applications.
  • Pb/Sn alloys There have been many historical reasons for the wide spread use of Pb/Sn alloys. These historical reasons include the low solidus temperature of Pb/Sn solder alloys, the workability of Pb/Sn alloys and of the resulting Cu/Sn intermetallics (formed at the solder/Cu contact interface) over a wide temperature range, the adhesion of Cu/Sn intermetallics obtained from Pb/Sn alloys to Cu lands and pads, and the ready availability of process equipment and low cost adjuncts, as resins, fluxes, and solder masks, for Pb/Sn alloys.
  • the relatively low temperatures required for processing Pb/Sn solder alloys are particularly important when polymeric dielectrics are used in the fabrication of electronic packages. These polymers can degrade in high temperature assembly operations. Solder alloys which melt at relatively low temperatures can accommodate these polymeric substrates.
  • softness or plasticity of lead based solders This softness or plasticity allows the solder to accommodate the mismatch in coefficients of thermal expansion between the bonded structures, for example the mismatch in coefficient of thermal of thermal expansion between a ceramic dielectric and a polymeric dielectric, or between a semiconductor chip and a ceramic or polymeric chip carrier or substrate.
  • lead is a toxic, heavy metal with a relatively high vapor pressure. Its use is disfavored, and a need exists for a replacement.
  • U.S. Pat. Nos. 4,643,875 and 4,667,871 to Howard Mizuhara for TIN BASED DUCTILE BRAZING ALLOYS describe high temperature brazing alloys containing from 35% to 95% Sn, from 0.5 to 70% Ag, from 0.5 to 20% Cu, effect amounts of one or more of Ti, V, and Zr, and optionally with Ni, and Cr.
  • the disclosed brazing alloys all require temperatures of at least 550 degrees Celsius for good bonding.
  • U.S. Pat. No. 4,806,309 to Stanley Tulman for TIN BASE LEAD-FREE SOLDER COMPOSITION CONTAINING BISMUTH, SILVER, AND ANTIMONY describes solder compositions containing from 90 to 95% Sn, from 3 to 5% Sb, from 1 to 4.5% Bi, and from 0.1 to 0.5% Ag. Tulman describes the use of Bi to lower the melting point of the solder to about 425 degrees F. (218 degrees C.).
  • the alloy contains at least about 90 weight percent Sn, with effective amounts of Ag, and Bi for thermal stability and strength.
  • the alloy contains Sb, and in a still further exemplification the alloy contains Sb and Cu.
  • the high solidus temperature, high service temperature, high strength multi-component solder alloy contains at least about 90 weight percent Sn and effective amounts of Ag, and Sb. Additionally, a small amount of bismuth may be present in the alloy.
  • the alloy contains at least about 90 weight percent Sn, with effective amounts of Ag, and Bi for thermal stability and strength.
  • One such alloy contains about 95.0 to 95.5 weight percent Sn, about 2.5 to 3.0 weight % Ag, and about 2.0 weight % Bi.
  • the alloy contains Sb.
  • One alloy, according to this exemplification of the invention contains about 93.5 to about 94.0 weight % Sn, about 2.5 to about 3.0 weight % Ag, about 1.0 to about 2.0 weight percent Bi, and about 1.0 to about 2.0 weight percent Sb.
  • the alloy contains Sb and Cu.
  • One particularly preferred Sn--Ag--Sb--Cu alloy is an alloy containing about 93.5 to about 94.0 weight % Sn, about 2.5 to about 3.0 weight % Ag, about 1.0 to about 2.0 weight percent Bi, about 1.0 to about 2.0 weight percent Sb, and about 1.0 weight percent Cu.
  • the high solidus temperature, high service temperature, high strength multi-component solder alloy contains at least about 90 weight percent Sn and effective amounts of Ag, and Sb.
  • One such high Sn alloy contains about 94.0 to 95.0 weight percent Sn, about 2.5 to 3.5 weight % Ag, and about 2.0 weight % Sb.
  • One such high Sn alloy contains about 93.5 to about 94.0 weight % Sn, about 2.5 to about 3.0 weight % Ag, about 1.0 to about 2.0 weight percent Bi, and about 1.0 to about 2.0 weight percent Sb.
  • solder alloy compositions of the invention are summarized in the Tables below:
  • a method of electrically connecting an integrated circuit chip to a circuitized substrate includes the step of depositing a solder alloy comprising at least about 90 weight percent Sn and either
  • solder alloy may be applied by wave solder deposition, electrodeposition, or as a solder paste.
  • the electrical leads of the circuitized substrate are then brought into contact with the solder alloy on the electrical contacts of the integrated circuit chip.
  • the current leads of the circuitized substrate are pads on the substrate, and the solder alloy deposits are brought into contact with the pads.
  • the current leads are wire leads, and tab inner lead connections, and they are brought into contact with the solder alloy contacts on the top surface of the integrated circuit chip.
  • the solder alloy While the substrate current leads and the solder deposits are maintained in contact the solder alloy is heated to cause the solder alloy to wet and bond to the electrical leads of the circuitized substrate. Heating may be by vapor phase reflow, infrared reflow, laser reflow, or the like.
  • the resulting microelectronic circuit package of the invention is an integrated circuit chip module with a circuitized chip carrier, i.e., a substrate, a semiconductor integrated circuit chip, and a solder bond electrical interconnection between the circuitized chip carrier and the semiconductor integrated circuit chip formed of a solder alloy comprising at least about 90 weight percent Sn and either
  • the alloys were tested to determine their creep properties.
  • the tensile strength of the alloy showed a projected rupture time of 70 days at 2500 psi and 23 degrees Centigrade.
  • the tensile strength was measured to be 59 (100 lbs/sq. inch), the yield strength was measured to be 31 (100 lbs/square inch), and the percent elongation was measured to be 35 percent.
  • the melting point of the alloy was measured to be 218 to 255 degrees Celsius.
  • the alloys were tested to determine their creep properties.
  • the tensile strength of the alloy showed a projected rupture time of 70 days at 2500 psi and 23 degrees Centigrade.
  • the alloys were also tested for cycle fatigue at 4.3 percent deflection at 23 degrees Celsius and five cycles per minute. Failure occurred after 60 cycles.
  • the melting point of the alloy was measured to be 200 to 224 degrees Celsius.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
US08/079,075 1993-06-16 1993-06-16 High temperature, lead-free, tin based solder composition Expired - Lifetime US5393489A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/079,075 US5393489A (en) 1993-06-16 1993-06-16 High temperature, lead-free, tin based solder composition
JP6081871A JPH0788680A (ja) 1993-06-16 1994-04-20 高温無鉛すずベースはんだの組成
KR1019940011318A KR970010891B1 (ko) 1993-06-16 1994-05-24 고온의 무연 주석 기재 납땜 조성물
EP94108683A EP0629466A1 (en) 1993-06-16 1994-06-07 High temperature, lead-free, tin based solder composition
TW083105956A TW363334B (en) 1993-06-16 1994-06-30 Lead-free, tin based solder composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/079,075 US5393489A (en) 1993-06-16 1993-06-16 High temperature, lead-free, tin based solder composition

Publications (1)

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US5393489A true US5393489A (en) 1995-02-28

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US08/079,075 Expired - Lifetime US5393489A (en) 1993-06-16 1993-06-16 High temperature, lead-free, tin based solder composition

Country Status (5)

Country Link
US (1) US5393489A (ko)
EP (1) EP0629466A1 (ko)
JP (1) JPH0788680A (ko)
KR (1) KR970010891B1 (ko)
TW (1) TW363334B (ko)

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997009455A1 (en) * 1995-09-01 1997-03-13 Sarnoff Corporation Soldering composition
US5658528A (en) * 1994-11-02 1997-08-19 Mitsui Mining & Smelting Co., Ltd. Lead-free solder
US5759379A (en) * 1996-04-26 1998-06-02 International Business Machines Corporation Solder method
US5833921A (en) * 1997-09-26 1998-11-10 Ford Motor Company Lead-free, low-temperature solder compositions
US5938862A (en) * 1998-04-03 1999-08-17 Delco Electronics Corporation Fatigue-resistant lead-free alloy
US5985692A (en) * 1995-06-07 1999-11-16 Microunit Systems Engineering, Inc. Process for flip-chip bonding a semiconductor die having gold bump electrodes
US6077477A (en) * 1996-06-06 2000-06-20 Matsushita Electric Industrial Co., Ltd. Solder alloy of electrode for joining electronic parts and soldering method
US6180264B1 (en) * 1998-09-14 2001-01-30 Murata Manufacturing Co., Ltd. Soldered article
US6187114B1 (en) 1996-10-17 2001-02-13 Matsushita Electric Industrial Co. Ltd. Solder material and electronic part using the same
US6224690B1 (en) * 1995-12-22 2001-05-01 International Business Machines Corporation Flip-Chip interconnections using lead-free solders
US6264093B1 (en) * 1998-11-02 2001-07-24 Raymond W. Pilukaitis Lead-free solder process for printed wiring boards
US6267823B1 (en) 1996-02-09 2001-07-31 Matsushita Electric Industrial Co., Ltd. Solder, solder paste and soldering method
US6416883B1 (en) * 1997-04-22 2002-07-09 Ecosolder International Pty Ltd Lead-free solder
US20030035976A1 (en) * 2001-08-14 2003-02-20 Strobel Richard W. Tin-silver coatings
US20030077588A1 (en) * 1996-10-04 2003-04-24 Chronix Biomedical, Inc Diagnostic detection of nucleic acids
US6569262B1 (en) 1999-02-23 2003-05-27 International Business Machines Corporation Lead-free solder powder material, lead-free solder paste and a method for preparing same
US6592020B1 (en) 2001-09-04 2003-07-15 Henkel Loctite Adhesives Limited Lead-free solder paste
US6648210B1 (en) * 1999-02-16 2003-11-18 Multicore Solders Limited Lead-free solder alloy powder paste use in PCB production
US6699306B2 (en) * 2000-02-24 2004-03-02 Nihon Superior Sha Co., Ltd. Control method for copper density in a solder dipping bath
US20040076541A1 (en) * 2002-10-22 2004-04-22 Laughlin John P. Friction-resistant alloy for use as a bearing
US20040151616A1 (en) * 2003-02-04 2004-08-05 Sabarese Daniel M. Lead-free alloys, composition thereof, methods of preparation and uses for soldering and babbitting
US6805974B2 (en) 2002-02-15 2004-10-19 International Business Machines Corporation Lead-free tin-silver-copper alloy solder composition
US20040217152A1 (en) * 2000-08-22 2004-11-04 Senju Metal Industry Co., Ltd. Lead-free solder paste for reflow soldering
US20050085062A1 (en) * 2003-10-15 2005-04-21 Semitool, Inc. Processes and tools for forming lead-free alloy solder precursors
US20060104855A1 (en) * 2004-11-15 2006-05-18 Metallic Resources, Inc. Lead-free solder alloy
US20070036671A1 (en) * 2003-04-25 2007-02-15 Hans-Jurgen Albrecht Soldering material based on sn ag and cu
US20080308300A1 (en) * 2007-06-18 2008-12-18 Conti Mark A Method of manufacturing electrically conductive strips
US20100143658A1 (en) * 2007-07-23 2010-06-10 Henkel Limited Solder flux
US20100214753A1 (en) * 1997-12-16 2010-08-26 Hanae Shimokawa Pb-free solder-connected structure and electronic device
CN101357421B (zh) * 2005-12-16 2010-12-29 浙江亚通焊材有限公司 无铅锡焊料
KR20160006667A (ko) 2013-05-10 2016-01-19 후지 덴키 가부시키가이샤 반도체 장치 및 반도체 장치의 제조방법
KR20160028015A (ko) 2014-09-02 2016-03-11 에이에치코리아주식회사 전자부품 실장용 무연땜납
US20180033761A1 (en) * 2015-09-17 2018-02-01 Fuji Electric Co., Ltd. Solder material for semiconductor device
CN113798731A (zh) * 2021-09-14 2021-12-17 上海大学 一种SP700钛合金用非晶Ti–Zr–Cu–Ni钎料合金、其制备方法和应用

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US6184475B1 (en) 1994-09-29 2001-02-06 Fujitsu Limited Lead-free solder composition with Bi, In and Sn
DE19538992A1 (de) * 1995-04-28 1996-10-31 Hewlett Packard Co Wismut-Zinn-Lötmittel-Verbindungen mit verbesserten mechanischen Eigenschaften
AU6333096A (en) * 1996-06-12 1998-01-07 International Business Machines Corporation Lead-free, high tin ternary solder alloy of tin, silver, and bismuth
JPH11291083A (ja) * 1998-04-14 1999-10-26 Murata Mfg Co Ltd 半田合金
WO2001036148A1 (fr) * 1999-11-18 2001-05-25 Nippon Steel Corporation Alliage de soudage, element electronique dote de globule et de bossage de soudure
TW453930B (en) * 2000-04-17 2001-09-11 Fujitsu Ltd Solder bonding
JP2014018859A (ja) * 2012-07-24 2014-02-03 Nippon Genma:Kk はんだ
JP2015077601A (ja) * 2013-04-02 2015-04-23 千住金属工業株式会社 鉛フリーはんだ合金
DE102022101056A1 (de) 2022-01-18 2023-07-20 STANNOL GmbH & Co. KG Verfahren zur Erzielung einer zuverlässigen Lötverbindung und Vorlegierungen hierfür

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Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5658528A (en) * 1994-11-02 1997-08-19 Mitsui Mining & Smelting Co., Ltd. Lead-free solder
US5985692A (en) * 1995-06-07 1999-11-16 Microunit Systems Engineering, Inc. Process for flip-chip bonding a semiconductor die having gold bump electrodes
WO1997009455A1 (en) * 1995-09-01 1997-03-13 Sarnoff Corporation Soldering composition
US6224690B1 (en) * 1995-12-22 2001-05-01 International Business Machines Corporation Flip-Chip interconnections using lead-free solders
US6428745B2 (en) 1996-02-09 2002-08-06 Matsushita Electric Industrial Co., Ltd. Solder, solder paste and soldering method
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TW363334B (en) 1999-07-01

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